CN103525298B - Thermostable anticorrosive coating and preparation method - Google Patents
Thermostable anticorrosive coating and preparation method Download PDFInfo
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- CN103525298B CN103525298B CN201310439813.6A CN201310439813A CN103525298B CN 103525298 B CN103525298 B CN 103525298B CN 201310439813 A CN201310439813 A CN 201310439813A CN 103525298 B CN103525298 B CN 103525298B
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Abstract
The invention relates to a kind of manufacture method of thermostable anticorrosive coating, this coating introduces amide group by double bond containing silane coupling agent, and then coupling agent and the silicone resin containing methoxyl group active group are carried out copolyreaction, prepare the modified organic silicone resin of amide-containing, itself and basic color is made to have extremely strong compatibleness, thus no longer react with alkali glass powder filler, this coating is made to have good stability in storage, and under the environment of 800 DEG C, namely there is high thermal resistance, also there is stronger etch-proof ability.
Description
Technical field
The invention belongs to technical field of chemical paint, relate to a kind of thermostable anticorrosive coating and preparation method, this coating is applicable to various high temperature resistant field, is particularly useful for the fire resistant anticorrosive field under 800 DEG C of environment.
Background technology
As everyone knows, the oxygen generation oxidizing reaction of metallic substance in hot environment easily and in air, produces corrosion phenomenon, thus makes metallic substance lose intensity gradually and cause structure properties to lack, become the hidden danger of various accident.Thermostable paint refers to that temperature is more than 800 DEG C; under the impact of high temperature and intensity; paint film is ablation not; still can keep suitable physical mechanical property; base material is effectively protected; such coating has purposes widely, its research has been become to a hot issue of advanced country's technical development in recent years.
At present for the high temperature oxidation and corrosion problem of metal; many employings fire-resistant oxidation resistant coating protection metal is the effective method of one reducing burning loss, and it is used widely at modern industry, military affairs, space industry etc. with easy to make, with low cost.Thermostable paint is the achievement of multidisciplinary combination and integrated application, and such coating can be widely used in the metallic high temperature protection etc. of high temperature steam pipeline, heat exchanger, condenser, High Temperature Furnaces Heating Apparatus, petroleum cracking equipment, motor part, metallurgy industry.For stove, China's steam boiler 1,000,000, Industrial Stoves 200,000, reverberatory furnace 500,000, large-scale resistance furnace 400,000.These stoves temperature in process of production generally reaches more than 600 DEG C, uses thermostable coating effectively to protect it, can reduce waste and the loss of the annual energy.
The 1950's starts, people drop into great effort research high-temperaure coating and coating, develop product miscellaneous, the product of resistance to less than 600 DEG C can be mainly modified organic silicon and inorganic silicon high-temperature resistant coating, can almost decompose completely the product organism of resistance to more than 600 DEG C, coated material is generally silico-aluminate, ceramic oxide etc., but required film-forming process is more complicated, need the somewhat expensives such as magnetron sputtering, electric arc spraying, plasma spray coating, be mainly used in most advanced and sophisticated scientific research and military field.Can the high-temperature resistant coating kind of heatproof 600 DEG C-800 DEG C for a long time little; and there is the problems such as Air drying difference (general requirement oven dry), resistance to elevated temperatures difference (come off, efflorescence, variable color etc.) in this type of coating of existing manufacturer production; and owing to differing about the technical evaluation of high-temperature resistant coating and standard; the deviation of high-temperaure coating failure cause analysis; cause the uneven problem of high-temperature resistant coating protected effect quite outstanding; therefore current a large amount of dependence on import, cost is high, the delivery cycle is long.This project have developed a kind of novel fire resistant protective system, inherits the advantage of traditional high-temperature resistant coating, not only long-term under 600-800 DEG C of hot environment use, and after hot environment, still have very high corrosion resistant performance.But along with the development of China's modern industry and deepening continuously of opening, the particularly industry such as metallurgy, petrochemical industry, the energy, novel material, novel process, new installation continue to bring out, to can resistance to 600-800 DEG C high temperature, high-temperature resistant coating demand simple, with low cost of constructing is very large, thus develop high performance can the high-temperature resistant coating application prospect of resistance to 600-800 DEG C high temperature boundless.
Summary of the invention
The object of the invention is to provide a kind of thermostable anticorrosive coating and preparation method.The present invention utilizes silicone resin to introduce amide group, makes resinite be tied to form neutral state, avoids the glass powder generation saponification reaction of Acid-Base System in coating.This thermostable paint is made not only to have fire resistant anticorrosive effect but also have good stability in storage.In silicone resin structure wherein, the thermodynamic stability .Si-C key of Si-O-Si key has good solidity, can improve coating heat resistance, add epoxide group improve resin snappiness, the sticking power of resin is improved greatly.The glass powder adding different melting points in coating system carries out composite, and can make this coating more than 600 DEG C, glass powder carries out melting, carries out two-step film forming, improves compactness and the rotproofness performance of coating.
The present invention is achieved by the following technical programs:
Formula: (being mass parts below)
Resin: 30 ~ 50
High-temperature resisting pigment: 30 ~ 50
Glass is black: 10 ~ 20
Glass white: 15 ~ 25
Filler: 10 ~ 25
Aluminium powder: 5 ~ 10
Auxiliary agent: 0 ~ 5
Solvent: 10 ~ 20
Wherein, coating resin used is N-hydroxyacrylamide modified organic silicone resin, and use the glass powder of different melting points as being melt into membrane substance, the heatproof rust-stabilising pigments such as enamel is black, aluminium powder, mica powder are as anticorrosive pigment/filler.
Modified organic silicone resin, is characterized in that free radical reaction occurs for both with between the amide-containing monomer containing unsaturated double-bond and the organosilane monomer containing unsaturated link(age), generates the organo-siloxane prepolymer containing amide group.Amide group monomer containing double bond is as N-hydroxymethylacrylate amine, DMAA, N-isopropylacrylamide etc.Organosilane monomer containing unsaturated link(age) is as vinyltriethoxysilane, methyl vinyl diethoxysilane, vinyl trichloro silane, methylvinyldichlorosilane, methacryloxypropyl trimethoxy silane (KH570).Should containing the organosilicon preformed polymer of amide group, to be hydrolyzed polycondensation with the siloxanes containing methoxyl group active function groups, finally to prepare the modified organic silicone resin being with amide group.
The present invention uses the glass powder of different melting points as being melt into membrane substance in coating, can after film forming after melting under high temperature as being melt into membrane substance, solve coating compactness problem, guarantee coating weather resistance at high temperature simultaneously.
A kind of preparation technology of fire resistant anticorrosive paint:
(1) modified organic silicone resin preparation
In the 1000ml four-hole boiling flask that agitator, thermometer are housed, drop into solvent, be warmed up to temperature of reaction, drip the organosilane monomer, amido compounds, initiator and the solvent solution that contain unsaturated link(age) respectively, at the uniform velocity drip off, add siloxanyl monomers and be incubated half an hour at assigned temperature, the obtained organosiloxane polymer containing amide group.
(2) high-temperature resistant silicone coating preparation
By mixing such as resin, pigment, filler and solvents after high speed dispersion 10min, sand milling, to fineness less than 50 microns, then adds auxiliary agent, obtains coating.By made coating application after workpiece, at 180 DEG C, solidification can reach optimum performance in 0.5 hour.
This coating introduces amide group by double bond containing silane coupling agent, and then coupling agent and the silicone resin containing methoxyl group active group are carried out copolyreaction, prepare the modified organic silicone resin of amide-containing, itself and basic color is made to have extremely strong compatibleness, thus no longer react with alkali glass powder filler, make this coating have good stability in storage, and under the environment of 800 DEG C, namely there is high thermal resistance, also there is stronger etch-proof ability.
Embodiment
One, starting material
Siloxanyl monomers industrial goods watt digest
1053 silicone resin industrial goods Zhong Hao morning twilight Chemical Co., Ltd.s
840 organic resin industrial goods DOW CORNING chemistry
Acrylamide monomer industrial goods Solution on Chemical Reagents in Shanghai company limited
Organo-silicon coupling agent industrial goods Nanjing dawn Chemical Co., Ltd.
Hexadecyl brometo de amonio chemical Jiangsu Jin Cheng reagent company limited
Thermo-stabilizer industrial goods Nantong Ai Dewang Chemical Co., Ltd.
2441 black industrial goods Shanghai Tianguang Chemical Factory of glass
2451 glass white industrial goods Shanghai Tianguang Chemical Factory
The black industrial goods Shanghai Tianguang Chemical Factory of enamel
Aluminium powder industrial goods Jinan metallic pigment company limited
Zinc phosphate industrial goods Shanghai Heng Zhan Chemical Co., Ltd.
Mica powder industrial goods Chuzhou Yang Tian split Engineering Co., Ltd
Talcum powder industrial goods Changzhou giant dragon powder Chemical Co., Ltd.
Two, specific embodiment
1, resin-made is standby: (adopting any one preparation in following method)
Method 1, in the 1000ml four-hole boiling flask that agitator, thermometer are housed, drop into xylene solvent 200ml. and be warmed up to 50 DEG C ~ 120 DEG C, drip methacryloxypropyl trimethoxy silane (KH570) 100ml, N hydroxymethyl acrylamide 50ml, hexadecyl brometo de amonio 10ml mixing solutions respectively, within 3 hours, at the uniform velocity drip off, add siloxanyl monomers 300ml again, 150 DEG C are incubated half an hour, the obtained organosiloxane resins containing amide group.
Method 2, in the 1000ml four-hole boiling flask that agitator, thermometer are housed, drop into xylene solvent 200ml. and be warmed up to 50 DEG C ~ 120 DEG C, drip DMAA 50ml, methyl vinyl diethoxysilane 100ml, hexadecyl brometo de amonio 10ml mixing solutions respectively, 3 hours all with drip off, add siloxanyl monomers 300ml again, 150 DEG C are incubated half an hour, the obtained organosiloxane resins containing amide group.
2, example prepared by coating
Production technique: by above-mentioned recipe requirements just resin, heatproof pigment, filler and solvent etc. mix and sand milling to fineness less than 50 microns, then add auxiliary agent, coating needed for obtained.
Making sheet requires: by the paint spay-coating that prepared on steel plate, solidifies 1 hour (dried film thickness controls at 40 ± 5 μm), under 800 DEG C of high temperature, then carry out the high temperature resistant experiment of 5 hours under 180 DEG C of high temperature.Model after high temperature resistant experiment carries out drawing by the relevant regulations in standard GB/T/T1771-2007 and to model to be pitched, and does salt spray resistance and detects.Detected result sees the following form.Stability in storage detects and measures by GB GB/T6753.3-1986.
As can be seen from the above table, use the temperature tolerance of the thermostable paint prepared of modified organic silicone resin, Corrosion Protection and storage stability all higher than high-temperature resistant coating prepared by general silicone resin, and the glass powder of this coating need fixing quantity.
Claims (2)
1. a thermostable anticorrosive coating, is characterized in that, in mass fraction, the formula of coating comprises:
Resin: 30 ~ 50,
High-temperature resisting pigment: 30 ~ 50,
The black 10-20 of glass,
Glass white 15-25,
Filler: 10 ~ 25,
Aluminium powder 5-10,
Auxiliary agent: 0 ~ 5,
Solvent: 10 ~ 20;
Described resin is N-hydroxyacrylamide modified organic silicone resin, modified organic silicone resin is, with between the amide-containing monomer containing unsaturated double-bond and the organosilane monomer containing unsaturated link(age), free radical reaction occurs, generate the organosilicon preformed polymer containing amide group, the organosilicon preformed polymer of amide group should be contained, to be hydrolyzed polycondensation with the siloxanes containing methoxyl group active function groups, finally to prepare the modified organic silicone resin of band amide group;
Amide-containing monomer wherein containing unsaturated double-bond is N hydroxymethyl acrylamide; Organosilane monomer containing unsaturated link(age) is selected from vinyltriethoxysilane, methyl vinyl diethoxysilane, vinyl trichloro silane, methylvinyldichlorosilane, methacryloxypropyl trimethoxy silane.
2. the preparation method of thermostable anticorrosive coating according to claim 1, it is characterized in that, concrete steps are as follows:
(1) modified organic silicone resin preparation
In the four-hole boiling flask that agitator, thermometer are housed, drop into solvent, be warmed up to temperature of reaction 50-120 DEG C, drip the organosilane monomer, amide group monomer, initiator and the solvent solution that contain unsaturated link(age) respectively, at the uniform velocity drip off, add siloxanyl monomers and be incubated half an hour at 150 DEG C, the obtained organosiloxane polymer containing amide group;
(2) high-temperature resistant silicone coating preparation
By resin, pigment, filler and solvent after high speed dispersion, sand milling, to fineness less than 50 microns, then adds auxiliary agent, obtains coating.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103881515B (en) * | 2014-03-11 | 2015-05-20 | 宁波科乐新材料有限公司 | Preparation method for super-hydrophilic organic silicon coating |
| CN106189396B (en) * | 2016-08-12 | 2018-02-13 | 福州布朗新材料技术有限公司 | A kind of high temp glass coating of resistance to aluminium liquid corrosion |
| CN106189397B (en) * | 2016-08-12 | 2018-02-13 | 福州布朗新材料技术有限公司 | A kind of anti-corrosion glass coating of aluminium liquid stirring high temperature resistant |
| CN106280586B (en) * | 2016-08-12 | 2018-02-13 | 福州布朗新材料技术有限公司 | A kind of anti-corrosion inorganic coating of aluminium liquid stirring high temperature resistant |
| CN116376344A (en) * | 2023-04-12 | 2023-07-04 | 上海航天精密机械研究所 | Room-temperature rapid-curing high-temperature-resistant gradient ceramic putty and preparation method thereof |
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| CN1217361A (en) * | 1997-11-13 | 1999-05-26 | 中国石油化工总公司 | Organosilicon modified propenoic acid emulsion paint |
| CN1528796A (en) * | 2003-09-28 | 2004-09-15 | 石油大学(华东) | Silicone modified polyacrylamide and preparing method thereof |
| CN101550315A (en) * | 2009-05-15 | 2009-10-07 | 泰州市四联化工有限公司 | Black organic-silicon heat-resisting paint and preparation method thereof |
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Patent Citations (3)
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| CN1217361A (en) * | 1997-11-13 | 1999-05-26 | 中国石油化工总公司 | Organosilicon modified propenoic acid emulsion paint |
| CN1528796A (en) * | 2003-09-28 | 2004-09-15 | 石油大学(华东) | Silicone modified polyacrylamide and preparing method thereof |
| CN101550315A (en) * | 2009-05-15 | 2009-10-07 | 泰州市四联化工有限公司 | Black organic-silicon heat-resisting paint and preparation method thereof |
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| 改性有机硅树脂涂料研究新进展;张玲等;《现代化工》;20061031;第26卷;全文 * |
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